Method of producing dyeings metallized with aluminum, manganese, iron, cobalt, nickel, copper, tin, and zirconium



Patented Aug. 22, 1950 METHOD OF PRODUCING DYEINGS METAL- LIZED IR ON: AND ZEECONIUM WITH ALUMINUM, MANGANESE, COBALT, NICKEL, COPPER, TIN,

George L. Royer, North Plainfield, and Chester A. Amick, Bound Brook, N. 3., assignors to American Cyanarnid Company,

New York,

N. Y., a corporation of Maine No Drawing. Application December 8, 1948, Serial No. 64,246

12 Claims.

This invention relates to a process for dyeing basic nitrogenous fibers such as wool with metallizable dyes and the salts of aluminum, manganese, iron, cobalt, nickel, copper, tin and zirconium to produce metallized dyeings on the fiber.

Many dyes having metallizable groups such as hydroxyl, carboxyl or amino, or azo dyes having salicyclic groups or anthraquinone dyes have been metallized with various heavy metals or rather polyvalent metals of which chromium is the most common. For this reason thes colors are sometimes referred to as chrome colors. Various processes have been used in dyeing metallized dyes such as forming the metal complex first and then dyeing; dyeing the goods and after treating with chromium compounds, the so-called top chrome process; and treating the goods with chromium compounds first and subsequently dyeing, the so-called bottom chrome process. These processes were unpopular because they required an additional step and so there was developed a process in which the metallization of the dye and the dyeing of the goods took place simultaneously in the same bath. This is called the metachrome process.

Some difficulty arose because the metachrome process depended on the dye penetrating the fiber before it became completely metallized. It was found in the past that cationic surface active agents increased penetration, but unfortunately they also reacted with the bath components to produce colored scum which resulted in uneven dyeings. In our prior Patent No. 2,434.178, there is described a metachrome process in which a colloidized cationic surface active agent was used which prevented scum formation and maintained any insoluble reaction products with a cationic surface active agent well dispersed in the dye bath. This process constituted a satisfactory solutionof the major difficulties in metachrome dyeing with chromium compounds.

According to the present invention basic nitrogenous fibers such as wool and silk are dyed from a single bath containing a metallizable dye,

a salt of aluminum, manganese, iron, cobalt, nickel, copper, tin and zirconium. and the salt of a metal of group 2 of the periodic system having an atomic weight less than that of mercury.

According to the present invention basic nitrogenous fibers such as wool and silk are dyed very level and in brilliant colors by subjecting the material to the action of a dye bath containing a metallizable dye and a soluble salt of the above metals. The colors obtained are en;

tirely different from those produced by the metachrome process in which metallization is effected with chromium as a metallizing metal.

While it has been possible as a laboratory curiosity to produce metal complexes of metallizable azo dyes with tin or zirconium, this has never been practicable nor has it been considered feasible to dye basic nitrogenous fibers such as wool from a single bath containing metallizable azo dyes and salts of the two metals in question. One of the reasons why it was thought that such a dyeing procedure would not be feasible is that the common salts of tin and to a somewhat lesser extent of zirconium, such as for example stannous and stannic chloride or zirconium sulfate, hydrolyze at higher temperatures in aqueous solution and are no longer completely soluble.

According to the present invention we have found that not only are shades of superior brilliancy and levelness obtainable by a single bath dyeing, but no problem is presented by the fact that the salts of tin and zirconium hydrolyze in the bath and are no longer completely soluble. W e have found that if surface active agents such as cationic surface active agents and non-ionic surface active agents are present, particularly if the cationic surface active agent is colloidized, the'products of hydrolysis of the metal salts remain in sufficiently fine dispersion so that the ions are available for reaction with the metallizable groups of the dyes and that in spite of the fact that the metallizing salts are not in complete solution or at least in complete molecular solution, shades of great levelness with high penetration and high brilliancy may be produced. It is not completely known why dispersed, partially hydrolyzed salts operate satisfactorily in the present invention and it is not intended to limit the invention to any theory of action. 'Ifhe smooth dyeing under circumstances favoring! hydrolysis of the metal salts is, however, a fact and an advantage of the present invention.

It is a further advantage of the invention that the general dyeing procedure follows accepted lines in the dyeing of chrome colors by the metachrorne process. It is thus unnecessary for the dyer to learn new techniques in order to obtain the advantages of the new colors made possible by the present invention.

While it is not essential in all cases that the surface active agents be colloidized, we prefer to use colloidized cationic surface active agents as improved levelness and best results are obtained under these conditions. However, the

invention is not limited thereto and suitable uncolloidized cationic agents, particularly when associated with non-ionic surface active agents, may b used.

In order to obtain the strongest shades and best penetration, we prefer to use another feature, namely a varying pH in the dye bath. The bath at the beginning of the dyeing is preferably alkaline with a pH not higher than 9.5 and is gradually changed during the dyeing to an acid ending up with a distinctly acid pH of about or less. This results in rapid penetration of the dye under the alkaline conditions where metal- ':'.ation is greatly reduced or eliminated followed by complete metallization of the uniformly fixed dye on the fiber when the bath is rendered more acid. This feature is an element of the preferred modification of the present invention. The change of the pH from alkaline to acid ma be effected by removing alkaline constituents such as volatile alkalies; for example; ammonia, or by the addition of' acids at later'stages of the dyeing. Any suitable acid may be used which does not interfere with the dyeing, acetic acid being particularly useful although a mineral acid such as hydrochloric acid and sulfuric acid' may also be employed.

It is an advantage of the present invention that it is usable generally withmost of the metallizable dyes which can be dyed by the metachrome process. However, there is some difference in readiness with which certain of the dyes produce metallized shades by" the present process and of course the process is of more interest in connection with the dyes which are readily susceptible to metachrome dyeing; However, it is an advantage of the invention that a general new class of dyeing is obtainable;

The invention will be described in greater detail in conjunction with the following specific examples which are typical illustrations. The

parts are by weight.

Example 1 A dye bath is prepared as follows: parts of a dye having Color Index No. 203, 10 parts of ammonium hydroxide, 5 parts of a non-ionic surface active agent prepared by reacting 2 mols polyethylene oxide (molecular Weight 4000) and 1 mol of a dimeriaed acid obtained by heat treating soya bean acid and distilling off the monomeric acid, parts of the condensation product of octad'ecylguani'dine bicarbonate and 6 parts of ethylene oxide, 50 parts of magnesium sulfate, 10 parts of stannic chloride and sufficient water to make up the bath to 40,000 parts.

The dye is preferably predissolved in boiling water before it is a ded to the bath to make it up to final concentration. 500' parts of woolen yarn or goods is prewet with water, then entered into the dye bath at 120 F. The dye liquor is gradually brought to the boil during about a half an hour with frequent turning of the wool to insure uniform dyeing. The boiling and turning are then continued for about a half an hour after which 10 parts of 28% acetic acid is added. After another half hour boiling and turning, 20 parts of 28% acetic acid are added and boiling continued for a third half hour. W001 dyed by this procedure has a strong, medium blue shade and the fibers are well penetrated; When the same material is dyed with a chromium salt in the metachrome process, a bluish black, s ad i Obtained.

Example 2 The procedure of Example 1 is repeated replacing the stannic chloride with the same quantity of stannous chloride. A similar strong blue shade is obtained.

Example 3 The procedure of Example 1 is followed replacing the stannic chloride with an equal weight of zirconium sulfate. A bluish red color is obtained and the wool fibers are uniformly penetrated.

Example 4 The procedure of Example 3 is repeated except that a dye having Color Index No. 652 is used. The wool is dyed a brilliant orange instead of the bluish red shade which is obtained when it is dyed by the ordinary metachrome process using chromium as the metallizing metal.

Example 5 The procedure of Example 4 is repeated, replacing the zirconium sulfate with. the same weight of stannous-sulfate. A very bright orange is obtained on the wool.

Example 6 The procedure of Example 5 is repeated substituting a dye having Color IndexNo. 343. The wool is dyeda bright yellow as contrasted with a light tan which is obtained when the dyeing is effected. by the metachrome process using chromium as the metallizing metal.

Example 7' A colleidized cationic. surface active agent is prepared by working one part of the condensation product of octadecylguanidine bicarbonate and six parts of ethylene oxide with four parts of corn dextrin prepared by dextrinizing corn starch: with h, hleric acid. The working is in a dough mixer with suflicient water to give a hick plastic magma. After mixing is complete the materiah is spread in thin layers in trays and dried in a vacuum ovenfollowed by grinding and screening through a 1-10 mesh screen.

The dyeing procedure'of Example 6 is followed, but the 7 parts of cationic and non-ionic surface active agent is replacedby the same amount of the colloidized cationic surface active agent described. above. The dyeing proceeds very smoothly and the same excellent results are obtained.

Example 8 The procedure of Example 5 is repeated substituting a dye having Color Index No. 202. The wool dyed inthis bath has a very bright cherry red color instead of the blue black color which is obtained with chromium by the metachrome process.

Example 9' The procedure of Example 8 is repeated but an equal amount of zirconium chloride replaces the stannous sulfate. The wool dyed from the bath has excellent lavender shade of good depth and the fibers are well penetrated.

Example 10 The procedure of Example 9 is repeated replacing the 50 parts of magnesium sulfate with 5 parts of calcium nitrate and using the dye of Example 4. The same bright orange dyeing results.

Example 11 The procedure of Example 1 is repeated replacing the magnesium sulfate with an equal weight of barium chloride. The results are similar to those obtained in Example 1.

Similar results are obtained when the same weight of zinc or cadmium nitrate is used instead of barium chloride. When the same weight of: zinc chloride is used a somewhat brighter and heavier shade is obtained.

Example 12 The procedure of Example 1 is repeated except the 50 parts of magnesium sulfate are replaced by 50 parts of cadmium chloride containing 2 /2 mols of Water of crystallization and the parts of stannic chloride are replaced with 10 parts of zirconium sulfate. A dyeing having good color value and excellent penetration of the fibers is obtained.

Example 13 The procedure of Example 12 is repeated except the dyeing is made on nylon. A good strong dyeing is obtained.

Example 14 The procedure of the preceding example is repeated except the dyeing is made on real silk. A good color value is obtained.

Example 15 The procedure of Example 1 is repeated except the color has 0.1. #1034. An excellent dyeing is obtained.

Example 16 100 parts of the condensation product of octadecylguanidine bicarbonate and six parts of ethylene oxide are colloidized by mixing with 400 parts of corn dextrin prepared by dextrinizing corn starch with hydrochloric acid, and the mixture is worked in a dough mixer with sufficient Water to give a thick plastic magma. After the mixing is complete, the material is spread in thin layers in trays and dried in a vacuum oven followed by grinding and screening through a 140 mesh screen.

A dye bath is prepared using 10 parts of the dye having Color Index No. 169 pre-dissolved in boiling water. 10 parts of 28% aqueous ammonium hydroxide, 12.5 parts of the colloidized cationic agent described above, 50 parts magnesium sulfate containing 7 mols of water of crystallization, and 12.5 parts of aluminum sulfate containing 18 mols of water of crystallization. The volume of the dye bath is made up to 40,000 parts with water. A control bath is prepared containing 10 parts of dye, 50 parts ammonium sulfate and 12.5 parts aluminum sulfate. The volume of this bath is likewise 40,000 parts.

500 parts of Wool are pre-wet with water and entered into each dye bath at 120 F. The dye liquor is gradually brought to the boil in half an hour with suflicient turning of the wool to insure uniform dyeing. Boiling and turning are continued for about half an hour whereupon 10 parts of 28% acetic acid is added. After another half hours boiling and turning, parts of 23% acetic acid are added and the boiling continued to make a total dyeing time of two hours. The wool is dyed a bright maroon shade instead of a typical violet shade obtained when the metallization is done with chromium in the ordinary metachrome process. spectrophotometric read- 6 ings show that the wool dyed in the bath containing the magnesium sulfate is 20% stronger than the control dyeing.

Example 17 Example 18 The procedure of Example 16 is followed, but a different dye is used being prepared by first coupling the diazo oxide of diazotized 2-aminol-nitrophenol to meta phenylene diamine and then coupling diazotized S-amino-naphthalenel-sulfonic acid to the monoazo dye. The wool is dyed a, rusty brown color and that dyed from the bath containing the preferred features is 20% stronger than the dyeing from the control bath.

Example 19 The procedure of Example 16 is followed, but the dye having Color Index No. 1034 is used. The wool is dyed a bright orange instead of the dull red which results from the ordinary metachrome process.

Example 20 The procedure of Example 16 is repeated with the dye having Color Index No. 292. The wool is dyed a brilliant deep blue instead of the green which is obtained by the ordinary metachrome process.

Example 21 Procedure of Example 16 is followed, but instead of using the same dye an equivalent amount of the dye prepared from diazotized sulfanilic acid coupled to orthohydroxybenzoic acid is used.

The wool is dyed a yellow as in the case of the metachrome process but the yellow is much brighter. Example 22 The procedure of Example 17 is repeated except that the parts of magnesium sulfate is replaced by five parts of calcium nitrate and parts of aluminum sulfate containing 18 mols of water of crystallization is used. The same bright maroon shade is obtained, the strength being 26% greater in the case of the bath containing calcium nitrate than in the control bath in which the salt is omitted.

Example 23 The procedure of Example 22 is repeated replacing the calcium nitrate with the weight of zinc chloride. The strength of dyeing is 30% greater than that of the control.

Example 24 The procedure of Example 22 is repeated replacing the calcium nitrate with the same weight of cadmium nitrate. An increase in strength of 22% is obtained over that of the control dyeing.

Example 25 The procedure of Example 16 is repeated except that the SOparts; of. magnesium sufiate: are replaced with 50 parts of cadmium chloride containing 2 mols of water of crystallization and the aluminum sulfate. is replaced by a stoichiometrically equivalent amount of aluminum chloride. An excellent brilliant red shade is obtained which has good penetration in the fiber.

Example 26 The procedure of Example 25' is repeated except the cadmium nitrate is replaced with barium chloride.

Example 2.7

The procedure of Example 25 is repeated except the dyeing is made on real silk. A beautitul bluish-red shade is obtained;

Example 28 The procedure of the preceding example is repeated except the dyeing is made on nylon. A bright red shade is obtained.

Example 29 The procedure of Example 16 was followed except that a dye having Color Index No. 203

was used and the aluminum sulfate was replaced by 50'parts of manganous sulfate. The wool is dyed a dark blue, thefibers showing good penetration.

Example 30 The dye bath is prepared as follows: 10 parts of a dye having Color Index No. 203 predissolved in boiling water, 10 parts of 28% aqueous ammonium hydroxicle 5 parts of a non-ionic surface active agent prepared by reacting 2 mols of polyethylene oxide (molecular weight 4000) and 1 mol of the dimeriaed acid obtained by heat treating soya bean acid and distilling off the monomeric acid, 2 parts of the condensation product of octadecyl guanidine bicarbonate, and 6 parts of ethylene oxide, 50 parts of magnesium sulfate-containing I8 mols of water of crystallization, 5 parts of cobaltous sulfate, sufficient water being added to bring up the volume of the bath to 40,000 parts, 500 parts of woolen yarn or piece goods is entered into the dye bath and dyed as described in Example 16'.

A control dyeing is made with the dye bath having parts of dyestufi predissolved in boiling water, 50 parts of ammonium sulfate and 5 parts of cobaltous sulfate. The volume of the bath being brought up to 40.000 parts. The dyeing procedure in the control bath is carried out as described in Example 16..

The material dyed in the bath contained magnesium sulfate and ammonia is 45% stronger than the control dyeing when measured on a recording spectrophotometer.

Example 31 The procedure of Example is repeated replacing the dyestuif with an equal amount of the dye having Color Index No. 98. The dyed shade is 55% stronger than that from the control bath.

Example 32 The procedure of Example 31 is followed using a different dye having Color Index No. 169 and the dyed shade is 18% stronger than the control dyeing.

Example 33 The procedure of Example 32 is followed using the dyestuff having Color Index No. 1034. The wool is dyed a brilliant blue shade instead of the fall 8 duller red shade which is; obtained .by the meta chrome process andv the dyed material, is 18% stronger than the control dyeing.

Example 34 The procedure of Example 33' is repeated but 10 parts of cobaltous chloride are used in place of the cobaltous sulfate. A deep brilliant shade of blue is obtained as in the preceding example but the strength 01' the dyeing is now 56% greater than the control dyeing.

Example The procedure of Example 34 is repeated substituting a dyestufi having Color Index No. 203. The dyed material is 35% stronger than the control dyeing.

Example 36 The procedure of Example 35 is repeated using 10 parts of ferric chloride in place of the cobaltous chloride. The dyed goods is 42% stronger than the control dyeing.

Example 37 The procedure of Example 36 is repeated but the dyestufi having Color Index No. 98 is substituted, and 10 parts of nickelous chloride is used in place of the ferric chloride. The goods dyed are 25% stronger than when dyed by the control method.

Example 38 The procedure of Example 37 is repeated but the 10 parts of nickelous chloride are replaced with an equal weight of copper sulfate. The dyeing is 18% stronger than the control dyeing.

Example 39 The procedure of Example 35 is repeated but 5 parts of calcium nitrate is used in place of 50 parts of magnesium sulfate. The color value of the dyeing made from the bath containing all of the ingredients is 50% stronger than the control dyeing.

Elrample 40 The procedure of Example 39 is repeated replacing the calcium nitrate with an equal weight of barium chloride. The wool dyed shows a 25% increase in strength over the control dyeing.

Example 41 The procedure of Example 39 is repeated re placing the calcium nitrate with an equal weight of zinc chloride. The wool dyed in this bath is s 39% stronger than the control dyeing.

Easample 42 The procedure of Example 39 is repeated substituting for the calcium nitrate an equal weight of cadmium nitrate. The strength of the wool dyed is 44% greater than the control dyeing.

Example 43 The procedure of Example 30 is repeated except 2.5% of the colloidjzed cationic agent described in Example 16 is used instead of the 1% non-ionic agent and 0.5% of the condensation product of octadecyl guanidine bicarbonate and ethylene oxide described in Example 38. Good color value and excellent penetration of the fiber s obtained.

Example 44 A colloidized cationic agent is prepared as in Example 16 except that the cationic product con- 7 taining mixed cctyl or stearylpyridinium halides is used in place of the condensation product of octadecyl guanidine bicarbonate and ethylene oxide. When this colloidized material is used with the color of the preceding example by the procedure of the preceding example, the sample dyed in the presence of the colloidized cationic agent has good color value and the fibers are well penetrated.

Example 45 A cationic agent consisting of a technical mixture of quaternary ammonium :bases containing the radicals of C15Hs1 and 0171-135 is colloidized by the procedure in Example 16. 2.5% of this colloidized material is substituted for the non-ionic and cationic surface active agents in Example 30 and the dyeing procedure carried out as in that example. The material dyed in the bath containing the magnesium sulfate, the colloidized surface active agents and the ammonium hydroxide showed excellent penetration into the individual fibers. If desired the surface active agent in this example may be replaced with an equal weight of diethyl amino ethyl stearyl amide acetate.

Example 46 The procedure of Example 30 is repeated except the color of Example 32 is used and the cobaltous sulfate is replaced by 2% cobaltous chloride containing 6 molecules of Water of crystallization. Dyeing was made on nylon and a good uniform shade was obtained.

Example 47 The procedure of the preceding example was repeated except the dyeing was made on real silk and a satisfactory strength and shade were obtained.

In the claims:

1. A method of dyeing which comprises subjecting substantially unmetallized basic nitrogenous fibers to the action of a dye bath formed by mixing a metallizable dye, a soluble metallizing salt selected from the salts of aluminum, manganese, iron, cobalt, nickel, copper, zirconium and tin, a soluble salt of a metal of group II of the periodic system having an atomic weight less than mercury, a water dispersible cationic surface active agent, water, and suflicient alkali to make the pH of the bath alkaline, but not higher than 9.5, and to cause said dye to react with said alkaline earth metal salt to form an alkaline earth complex of said dye, partially dyeing said fibers from said complex, gradually lowering the pH of said bath at least to the point where decomposition of said complex and metallization of the dye take place, and completing the dyeing at said lowered pH.

2. A method according to claim 1 in which the final pH is distinctly acid.

3. A method according to claim 2 in which the metallizable salt is a salt of aluminum.

4. A method according to claim 3 in which the alkaline earth metal salt is magnesium sulfate.

5. A method according to claim 2 in which the metallizable salt is a salt of manganese.

6. A method according to claim 5 in which the alkaline earth metal salt is magnesium sulfate.

7. A method according to claim 2 in which the metallizable salt is a salt of cobalt.

8. A method according to claim 7 in which the alkaline earth metal salt is magnesium sulfate.

9. A method according to claim 2 in which the metallizable salt is a salt of nickel.

10. A method according to claim 9 in which the alkaline each metal salt is magnesium sulfate.

11. A method according to claim 2 in which the metallizable salt is a salt of zirconium.

12. A method according to claim 11 in which the alkaline earth metal salt is magnesium sulfate.

GEORGE L. ROYER. CHESTER A. AMICK.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 941,399 Winslow Nov. 30, 1909 1,511,359 Onnertz Oct. 14, 1924 2,434,178 Royer Jan. 6, 1948 2,443,166 Millson June 8, 1948 OTHER REFERENCES Amer. Dyes. Reporter for Sept. 8, 1947, page P495. 

1. A METHOD OF DYEING WHICH COMPRISES SUBJECTING SUBSTANTIALLY UNMETALLIZED BASIC NITROGENOUS FIBERS TO THE ACTION OF A DYE BATH FORMED BY MIXING A METALLIZABLE DYE, A SOLUBLE METALLIZING SALT SELECTED FROM THE SALTS OF ALUMINUM, MANGANESE, IRON, COBALT, NICKEL, COPPER, ZIRCONIUM AND TIN, A SOLUBLE SALT OF A METAL OF GROUP II OF THE PERIODIC SYSTEM HAVING AN ATOMIC WEIGHT LESS THAN MERCURY, A WATER DISPERSIBLE CATIONIC SURFACE ACTIVE AGENT, WATER, AND SUFFICIENT ALKALI TO MAKE THE PH OF THE BATH ALKALINE, BUT NOT HIGHER THAN 9.5, AND TO CAUSE SAID DYE TO REACT WITH SAID ALKALINE EARTH METAL SALT TO FORM AN ALKALINE EARTH COMPLEX OF SAID DYE, PARTIALLY DYEING SAID FIBERS FROM SAID COMPLEX, GRADUALLY LOWERING THE PH OF SAID BATH AT LEAST TO THE POINT WHERE DECOMPOSITION OF SAID COMPLEX AND METALLIZATION OF THE DYE TAKE PLACE, AND COMPLETING THE DYEING AT SAID LOWERED PH. 